JP4080434B2 - Degassing method - Google Patents

Description

The present invention relates to a degassing method using the deaerator filler used in the degassing of gas components dissolved in the liquid in the production or the like of pure water, filling deaerator treated reformed with ozone The present invention relates to a deaeration method using a material and a filler for a deaeration device manufactured by the reforming process .

  In water treatment in the fields of electronic products such as semiconductors and liquid crystals, pharmaceuticals, and foods, pure water with few impurities plays an extremely important role, and a pure water production apparatus is used to supply the pure water.

  Since the reverse osmosis membrane (RO) used in the reverse osmosis membrane device which is the main device of this pure water production device and the ion exchange resin used in the ion exchange device are oxidized and deteriorated by dissolved oxygen in the water, The manufacturing apparatus incorporates a vacuum degassing apparatus or the like in the preceding stage of these apparatuses.

  This vacuum deaerator usually contains a filler, and improves the deaeration efficiency of dissolved oxygen and the like in the liquid. In addition to this, it has also been proposed to improve the deaeration efficiency by providing a gas-liquid contact increasing material (demister) on the upper part of the filler filled in the vacuum deaerator (see, for example, Patent Document 1). ).

In addition, in gas-liquid contact fillers such as heat exchange fillers and deodorizing fillers, a filler with a large specific surface area of the filler is used in order to improve processing performance, or this is stored in multiple stages and contacted. Increasing efficiency is usually performed (for example, refer to Patent Document 2).
JP-A-6-55164 JP 2002-153725 A

  However, in the case of using the gas-liquid contact increasing material, the number of parts of the deaeration device increases, and when increasing the specific surface area of the filler, a specific material must be used. What is stored is not preferable because it is necessary to increase the size of the storage section because the storage section needs to be enlarged, and the number of parts increases.

  Therefore, the present invention increases the effective area without forming the dead face, which is a feature of the resin filler, has a small pressure loss with a linear structure, is lightweight, and retains chemical and mechanical properties. An object of the present invention is to provide a method for modifying a filler for a degassing apparatus and a filler for a degassing apparatus that increase the contact efficiency and thereby improve the degassing efficiency of the dissolved gas in the treated water.

The deaeration method of the present invention is a deaeration method using a filler for a deaerator , wherein a resin constituting the filler for a deaerator is previously brought into contact with ozone water before deaeration. Degassing is performed using the obtained filler for a degassing apparatus .

In addition, the degassing device filler according to the present invention is characterized in that the degassing device filler is treated in advance by a reforming treatment method in which a resin constituting the degassing device filler and ozone water are brought into contact with each other. Is.

In the degassing method of the present invention, before degassing, the resin constituting the filler for degassing device is brought into contact with ozone water in advance , and degassing is performed using the degassing device filler obtained by the contact. As the resin constituting the filler for the degassing device used here, any resin that is thermosetting or thermoplastic can be used as long as the degassing performance can be improved by ozone gas. It can also be used.

  Among these, from the viewpoint of economic efficiency, a thermoplastic resin is preferable from the viewpoint of easy molding. Examples of the thermoplastic resin include polyethylene (PE), polypropylene (PP), and polyvinyl chloride ( PVC) and the like, and is preferably a resin containing at least one selected from these resins.

  In addition, as the resin for performing the ozone treatment, a resin that has been conventionally used as a filler for a deaerator, that is, a resin that has been molded as a filler, is a resin that becomes a material before molding of the filler. There may be.

  Next, the modification treatment method of the present invention can be achieved by bringing such a resin into contact with ozone water.

  The ozone water used at this time can be manufactured using commercially available products such as an ozone gas generator that generates ozone gas and an ozone water generator that dissolves the generated ozone gas in pure water. As the water used as the raw material for the ozone water, pure water obtained by a method such as ion exchange, distillation, reverse osmosis or the like is used, but tap water or the like may be mixed within a range where a necessary ozone concentration can be obtained.

  In addition, within the range where ozone concentration in ozone water does not become unstable, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, alkali agents such as sodium hydroxide and potassium hydroxide, organic solvents such as alcohol, etc. It can also be added. The ozone concentration of the ozone water is not particularly limited as long as it has the effect obtained in the present invention, but is preferably in the range of 10 to 70 mg / L.

  Although it does not specifically limit regarding the processing temperature of ozone water, It is preferable that it is 50 degrees C or less, when it considers that decomposition | disassembly of ozone is accelerated and it becomes difficult to maintain a density | concentration when the temperature of ozone water becomes high. It is particularly preferred.

  The contact time between the resin and the ozone water depends on conditions such as the material of the base material and the ozone concentration of ozone water, and is not particularly limited, but when used in the above preferred ozone concentration range, While preventing resin deterioration due to rapid oxidation by ozone, it is necessary to modify the surface of the resin, and it is preferable to bring it into contact slowly for a long time, for example, about 1 day or more and 6 days or less.

Moreover, the filler for deaerators of this invention is manufactured using the modification process of the filler used for the deaeration method of this invention. This degassing device filler can be produced simply by ozone treatment if the resin is molded into a filler shape before the reforming treatment. When the ozone treatment is performed, the resin can be produced by molding the modified resin into the shape of the filler.

  If the resin molded into a filler shape is to be treated with ozone, a commercially available filler can be used as a raw material, and after the modification treatment, the resulting filler is immediately an excellent degassing device. It is preferable at the point which can be used as a filler.

By using the degassing method of the present invention, the degassing device filler having improved degassing efficiency can be used even if the filler material has the same shape as the conventional one, so that efficient degassing treatment can be performed . Therefore, according to this reforming treatment method, the amount of the filler can be reduced, the deaerator can be downsized, and the pure water production apparatus itself can be made compact. In addition, since the amount of filler used for exhibiting the same performance as the conventional one is small, the running cost can be suppressed.

  In addition, when the same amount of filler as in the prior art is used, the amount of dissolved oxygen in the treated water can be further reduced. Therefore, a reverse osmosis membrane (RO membrane) disposed downstream of the deaeration device in the pure water production device. ), Which is useful for preventing oxidative degradation of ion exchange resins and the like.

  Hereinafter, the reforming method for a filler for a deaerator according to the present invention will be described in detail with reference to the drawings.

(First embodiment)
FIG. 1 is a schematic diagram showing a processing apparatus used in the first embodiment in the method for reforming a filler for a degassing apparatus used in the degassing process according to the present invention.

  This processing apparatus includes an electrolytic gas generator that generates ozone gas by electrolysis and an ozone treatment tank.

  The ozone gas and hydrogen gas generator 1 of the electrolytic gas generator is provided with an ion exchange membrane 1a, and a porous anode material 1b and a cathode material 1c are arranged in close contact with both ends of the ion exchange membrane 1a. By electrolyzing the ion exchange membrane 1a as a solid electrolyte, ozone gas and oxygen gas are produced from the anode side, and hydrogen gas is produced from the cathode side.

  Pure water 3 is supplied to the ozone gas and hydrogen gas generator 1. A power source 2 is connected to the generator 1, and gas is generated by current from the power source 2.

  The generated ozone and hydrogen gas are separated by the gas separation units 4 and 5, respectively, and led to the ozone gas conduit 9 and the hydrogen gas conduit 10.

  The ozone gas led to the ozone gas conduit 9 is released from the ozone diffuser 12 through the ozone gas pipe 15 and is dissolved in pure water stored in the treatment tank 11 for immersing the filler to generate ozone water. To do. The ozone water in the treatment tank 11 is kept at a uniform ozone concentration by the ozone water circulation pump 13 and the ozone water circulation pipe 14 for returning the ozone water to the treatment tank uniformly.

  In addition to this electrolytic gas generator, there are well known ozone gas generation methods such as a silent discharge method that generates ozone gas by applying a high-frequency high voltage, and an ozone generation method that uses ultraviolet (UV). Like the gas generator, ozone water can be generated by supplying ozone gas to the treatment tank 11.

  After the treatment tank 11 is filled with ozone water in this way, the degassing filler used for the reforming process is immersed in the treatment tank 11 and contact treatment with ozone water is performed at a predetermined temperature and time. Thus, the method for reforming a filler for a deaerator according to the present invention can be achieved.

  In addition, it is considered as one of the mechanism of action that the degassing efficiency of the degassing device filler obtained by the reforming method using ozone water of the degassing device filler of the present invention is significantly improved. This is probably because the resin surface is modified from hydrophobic to hydrophilic.

  Further, the concentration of ozone gas sent through the ozone gas pipe 15 is maintained by stable voltage control of the DC power supply 2. Since the ozone gas concentration is attenuated by the transport distance, the ozone gas pipe 15 to the processing tank 11 is preferably as short as possible.

(Second Embodiment)
Further, the second embodiment of the method for reforming a filler for a deaerator used in the deaeration process according to the present invention is different only in the means for generating high-concentration ozone gas in the electrolysis gas generator. Other configurations are performed by using the same processing apparatus as in the first embodiment.

  As shown in FIG. 2, the electrolysis gas generator for generating high-concentration ozone gas in this embodiment supplies carbonated water in place of the pure water supplied to the anode side in the first embodiment. The carbon dioxide gas contact mechanism 8 is attached to the pure water water supply pipe 3 on the anode side, and carbon dioxide gas is permeated and dissolved in pure water from the gas-liquid contact film of the carbon dioxide gas contact mechanism 8.

  In the present embodiment, pure water comes into contact with carbonic acid to become carbonated water. Therefore, in the case of pure water with high purity, carbonated water is supplied, and ozone generated at the anode is lowered by reducing the pH. Ozone decomposition can be prevented and decrease in ozone concentration can be suppressed. Also, in the case of pure water containing hydrogen peroxide, hydrogen peroxide in pure water is stripped by carbon dioxide gas and supplied to the anode side, so ozone generated at the anode is peroxidized in pure water. There is no consumption with hydrogen.

  Further, before pure water comes into contact with carbon dioxide gas to form carbonated water, pure water can be once brought into contact with ozone gas to form ozone water, and then contacted with carbon dioxide gas again to be supplied as carbonated water. In such a case, in the case of pure water containing hydrogen peroxide, hydrogen peroxide in the pure water is once oxidized and decomposed by ozone gas, and then supplied to the anode side as stable water having a low pH by carbon dioxide gas. Therefore, ozone generated at the anode is generated as a high-concentration ozone gas that is not affected by pure water.

  At this time, the amount of carbon dioxide gas in contact with pure water supplied to the anode side before supply should be controlled in a range of 0.5 to 15% with respect to ozone and oxygen generation gas. When the amount is small, the pH is not lowered and the generation of ozone is not stable, and when it exceeds 15%, the ozone water in the anode chamber is stripped by carbon dioxide gas and the ozone gas concentration does not rise. Furthermore, in order to stably maintain the ozone gas concentration at a high concentration, it is desirable that the amount of carbon dioxide gas is controlled within a range of 2.5 to 10% with respect to the generated gas of ozone and oxygen.

  There are various methods for contacting the pure water supplied to the anode and the carbon dioxide gas that comes into contact before the supply. Generally, carbon dioxide gas is mixed with pure water using an ejector or static mixer. , A method in which carbon dioxide gas is diffused from a diffuser plate and carbon dioxide gas is dissolved in pure water. Carbon dioxide gas is dissolved in pure water through a membrane by introducing pure water into one side through a membrane and carbon dioxide gas into the other. A method of making it possible is conceivable.

  In the electrolytic gas generator, the ozone concentration of ozone water in the ozone gas generator 1 is 10 ppm on average in the case of pure water supply, whereas the ozone concentration of ozone water in the ozone gas generator 1 in the case of carbonated water supply. Can be obtained at a high concentration of 70 ppm on average. Therefore, by supplying the high-concentration ozone gas once taken out from the ozone water, the high-concentration ozone water is obtained in the treatment tank 11 and the filler can be easily modified. In this case, the reforming treatment can be performed efficiently, which is economically advantageous as compared with the supply of pure water.

  Hereinafter, the present invention will be described in detail based on examples.

Example 1
In Example 1, the measurement was performed using the apparatus having the configuration shown in FIG.
First, in the processing tank 11 (water tank dimensions: depth 850 mm × width 5900 mm × height 650 mm (effective water depth 500 mm)) of the degassing device filler, the product for degassing device (manufactured by Nippon Steel Chemical Co., Ltd., product) Name: Terralet) was added to 1.5 m ³ (100 L / bag × 15 bags), and pure water was injected to an effective water depth of 500 mm. While circulating at a rate of 3 m ³ / min with an SUS-316 ozone water circulation pump 13 (1 kW), 1.8 L of generated gas with an ozone concentration of 10% obtained by supplying pure water to the anode side with an electrolysis gas generator The gas was diffused and dissolved in the treatment tank 11 from the ozone gas diffusing tube 12 (caliber: 25A, length: 2 m, 2 tubes) at / min. After confirming that the ozone concentration of the ozone water in the treatment tank 11 was 10 ppm on average, it was treated for 4 days (136 hours) as it was, and then taken out from the treatment tank 11 and naturally dried. In addition, as the material of terralet, the same treatment was performed for three types of polypropylene (PP), polyethylene (PE), and polyvinyl chloride (PVC).

  The performance of the filler for the degassing device obtained by the ozone treatment was measured using the dissolved oxygen degassing treatment experimental device in pure water shown in FIG. 3, and the results are shown in Table 1.

In addition, the dissolved oxygen deaeration treatment experimental apparatus used at this time has a tower diameter: 150 mmφ, a total length: 4500 mm, a water height in the tower: 30 to 50 mm, a packed bed height: 2200 mm (filled quantity: 35 L), and an upper layer height: 1000 mm. , Lower layer height: 1000 mm, a deaeration tower 16 and an accompanying manometer 17, a tap water-sealed vacuum pump 18 and a pressure gauge pump 19 for blowing nitrogen gas, and a dissolved oxygen meter provided at the outlet of the degassed water (DO meter) 20 and a specific resistance meter (DO meter) 21, and measured by injecting pure water having a specific resistance of 17 MΩ / cm from the inlet at a water amount of 0.5 m ³ / hr. It is what I did.

 As shown in Table 1, the degassing filler that was treated with ozone water had a degassing efficiency nearly double that in a normal state in which nitrogen gas was not encapsulated, compared with those that were not ozonized, and nitrogen gas was encapsulated. In some cases, the deaeration efficiency was nearly three times.

(Example 2)
In Example 2, the measurement was performed using the apparatus having the configuration shown in FIG.
In the present embodiment, the same apparatus as that of the first embodiment is used except for the means for generating high-concentration ozone gas in the electrolysis gas generator.

  In order to generate high-concentration ozone gas, carbonated water is added to the anode side instead of ultrapure water. Carbonated water is produced by dissolving carbon dioxide in the ultrapure water from the carbon dioxide contact mechanism 8. In this embodiment, the amount of carbon dioxide injected into the carbon dioxide contact mechanism 8 is the amount of ozone and oxygen generated. It was set to 126% / min, 7% for 1.8 L / min. Carbon dioxide gas was blown in, and the generated carbonated water was supplied to the anode side from the water pipe 3 and added, whereby high-concentration ozone gas with an ozone concentration of 20% was generated. When this gas was supplied to the ozone gas diffusing tube 12 in the same manner as in Example 1, ozone water having an average ozone concentration of 25 ppm could be confirmed in the treatment tank 11. In this case, a filler having the same degassing efficiency as in Example 1 could be obtained by ozone treatment in a short time of 1.5 days (about 35 hours).

The filler modified by the degassing resin filler modification treatment method used in the degassing method of the present invention can be used as an exhaust gas cleaning filler or as a filler. Can greatly contribute to mitigation.

It is a conceptual diagram of the processing apparatus used for 1st Embodiment by the modification | reformation processing method of the filler for deaerators which concerns on this invention. It is a conceptual diagram of the processing apparatus used for 2nd Embodiment by the modification | reformation processing method of the filler for deaerators which concerns on this invention. It is a conceptual diagram of the dissolved oxygen deaeration processing experiment apparatus in the pure water used for the deaeration efficiency measurement of the deaeration filler in an Example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Generation | occurrence | production part of ozone gas, hydrogen gas, 1a ... Ion exchange membrane, 1b ... Porous anode material, 1c ... Porous cathode material, 2 ... DC power supply, 3 ... Pure water water pipe, 4 ... Ozone gas separation part, DESCRIPTION OF SYMBOLS 5 ... Hydrogen gas separation part, 6 ... Carbonated water feed pipe, 7a ... Carbon dioxide gas exhaust pipe, 7b ... Carbon dioxide gas injection pipe, 8 ... Carbon dioxide gas contact mechanism, 9 ... Ozone gas conduit, 10 ... Hydrogen gas conduit, 11 ... Treatment tank DESCRIPTION OF SYMBOLS 12 ... Ozone gas diffusion pipe, 13 ... Ozone water circulation pump, 14 ... Ozone water circulation pipe, 15 ... Ozone gas pipe, 16 ... Packing tower, 17 ... Manometer, 18 ... Tap water enclosed vacuum pump, 19 ... Nitrogen gas blowing pressure gauge Pump, 20 ... dissolved oxygen meter (DO meter), 21 ... specific resistance meter (DO meter)

Claims (3)

  In the degassing method using the degassing device filler, before degassing, the resin constituting the degassing device filler is previously brought into contact with ozone water, and the degassing device filling obtained by the contact is made. A degassing method comprising degassing using an agent.   The degassing method according to claim 1, wherein the ozone concentration in the ozone water is 10 to 70 mg / L.   The degassing method according to claim 1 or 2, wherein the resin is a resin containing at least one selected from polyethylene, polypropylene, and polyvinyl chloride.

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